JP2003234104A - Carbon black for electrode of battery or electric double layer-type capacitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbon black for an electrode of a battery or an electric double layer-type capacitor wherein the battery or the electric double layer-type capacitor superior in a capacity, heavy loading characteristic, and cycle characteristic can be manufactured. <P>SOLUTION: This is the carbon black used as the electrode composition of the battery or the electric double layer-type capacitor, and the micropore width is in a range from 4.0 to 8.0 Å and the maximum value of the micropore volume is from 0.060 to 0.135 ml/Å/g when the micropore volume led from a relational curve between a micropore volume and a micropore width becomes to have the maximum value. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a primary battery such as a lithium battery, a manganese battery, an alkali manganese battery, a lithium ion battery, a lithium polymer battery, an air zinc battery, a nickel hydrogen battery, a polymer battery, a sodium sulfur battery. , Carbon black used as an electrode composition of secondary batteries such as zinc bromine batteries and electric double layer capacitors.

[0002]

2. Description of the Related Art In recent years, development of high-performance batteries and high-performance capacitors has been actively promoted in response to demands for smaller and lighter electronic devices, multifunctionalization, and cordlessness. Batteries can be divided into single-use type primary batteries and secondary batteries that can be repeatedly used by charging. Examples of the former include organic electrolyte batteries (such as lithium primary batteries) using light metals and manganese dioxide, manganese primary batteries,
Examples of the latter are alkaline manganese primary batteries. Examples of the latter are alkaline secondary batteries using hydrogen storage alloys (such as nickel-hydrogen secondary batteries) and non-aqueous electrolyte secondary batteries using lithium compounds (lithium ion secondary batteries). Batteries, etc.), lithium polymer secondary batteries, air zinc secondary batteries, polymer secondary batteries, sodium-sulfur secondary batteries, zinc-bromine secondary batteries, and the like. Further, as the capacitor, an electric double layer type capacitor of a type in which an electric charge is retained and utilized on the surface of an activated carbon-based carbon material can be mentioned.

As a part of higher performance, carbon black is often used as a carrier material for efficiently transporting electrons generated from compounds used as active materials of various batteries and electric double layer type capacitors to a current collector. To be

As an example, a case of a lithium ion secondary battery will be described.

The lithium ion secondary battery uses a lithium-containing composite oxide of a transition metal as a positive electrode active material, that is, LiMO ₂ having a layered structure or LiM ₂ O ₄ having a spinel structure (where M is a transition metal such as cobalt. , Manganese, nickel, or iron) and the like, and a carbon material that occludes lithium ions to form an intercalation compound as a negative electrode material, and one of the lithium ions released between the positive electrode and the negative electrode Charging / discharging is performed by a reversible reaction of occluding. Research is underway to further increase the capacity and improve the heavy load characteristics of lithium-ion secondary batteries. Since the lithium composite oxide used as the positive electrode material here has low performance as an electron carrier material, it is generally used as a positive electrode by incorporating an electron carrier material such as carbon black.

However, a carbon black type electron carrier material (acetylene black etc.) which has been widely used in the past.
Has higher capacity and improved heavy load characteristics than a system that does not use carbon black, but has not yet achieved satisfactory performance.

To solve this problem, for example, Japanese Patent Laid-Open No. 11-4
No. 0139 discloses a specific dibutyl phthalate (DB
P) A carbon black that has an oil absorption amount and that has a specific resistance when pressed in a dry state is limited to 10 Ω · cm or less is proposed. However, although the specific resistance that is pressed in the dry state is an index of the conductivity of carbon black itself,
In the present situation, the conductivity when a certain amount of carbon black is contained in the system is not reflected, and it does not directly lead to the improvement of the above problems.

Further, in JP-A-2001-167767, a DBP oil absorption of 100 to 1 is used as a positive electrode mixture component.
Although a method of using 000 ml / g of carbon black to improve the capacity and the cycle characteristics at high temperature has been proposed, it has not yet reached satisfactory performance.

The same applies to batteries other than lithium-ion secondary batteries and electric double layer capacitors. For example, in the case of lithium-manganese dioxide batteries, the positive electrode is described in JP-A-63-960 and JP-A-2-155168. A method of increasing discharge voltage by using carbon black having a graphitized structure as a conductive material in a mixture has been proposed. Further, in a nickel-hydrogen secondary battery, Japanese Patent Laid-Open No. 2000-123
Japanese Patent No. 832 proposes a method of using crushed carbon black as a conductive agent to produce an electrode having excellent rapid discharge characteristics.

Further, in the electric double layer type capacitor,
In Japanese Unexamined Patent Publication No. 5-326327, an activated carbon-sulfuric acid kneading body is housed in a flat bag of conductive rubber, an electrode is formed using this bag as a current collector, and the bag is inserted into a plastic battery case having a partition wall. A method for producing an electric double layer capacitor having a low resistance has been proposed. In addition, JP-A-9-275
Japanese Patent Publication No. 041 has proposed a method of increasing the capacity by forming a polarizable electrode using carbon black having a specific surface area of 1000 m ² / g or more, but further capacity, heavy load characteristics, cycle Improvement of characteristics is desired.

[0011]

The present invention has been made to solve the above-mentioned problems, and is a carbon black used as an electrode composition of a battery or an electric double layer type capacitor, which has characteristics of capacity and heavy load. An object of the present invention is to provide a carbon black capable of producing a battery or an electric double layer type capacitor having good cycle characteristics.

[0012]

In order to achieve the above-mentioned object, the inventors of the present invention are concerned with what kind of properties are suitable for the carbon black used in this application. As a result of repeated intensive studies focusing on the volatile composition resulting from the functional group, carbon black having a specific micropore shape and pore volume is used for batteries,
The inventors have found that the capacitor performance is improved and have completed the present invention.

Therefore, the present invention is a carbon black used as an electrode composition of a battery or an electric double layer type capacitor, in which the maximum value of the micropore volume derived from the relationship curve between the micropore volume and the micropore width is the maximum value. Where the micropore width is within the range of 4.0 to 8.0 angstrom, and the maximum value of the micropore volume is 0.0
A carbon black for an electrode of a battery or an electric double layer type capacitor, which is characterized in that the amount is 60 to 0.135 ml / angstrom / g.

In the above, the maximum value of the micropore volume of carbon black is 0.075 to 0.135 ml /
It is preferably angstrom / g, more preferably 0.090 to 0.135 ml / angstrom / g.
It should be g.

In the carbon black for electrodes, the total pore volume is preferably 3.5 to 5.0 ml / g, and the total pore volume is 4.0 to 5.0 ml / g. Is more preferable. The ratio of carbon monoxide / carbon dioxide (hereinafter, “CO / CO ₂ ”) of volatile matter at 950 ° C. of the carbon black is preferably in the range of 6.0 to 10.0. By defining the pore characteristics and the surface functional group characteristics in this way, it is possible to enhance the capacity, heavy load characteristics, and cycle characteristics of the battery and the electric double layer type capacitor.

From the above viewpoint, therefore, as the carbon black characteristics, the micropore width is in the range of 4.5 to 7.5 angstrom and the maximum value of the micropore volume is 0.095 to 0.130 ml. / Angstrom / g
And the total pore volume is 4.1-4.9 ml / g, CO / CO
₂ is more preferably 6.5 to 9.5, and particularly,
The micropore width is in the range of 5.0 to 7.0 angstrom and the maximum value of the micropore volume is 0.100 to
It is even more preferred that the total pore volume is 0.125 ml / angstrom / g, the total pore volume is 4.2 to 4.8 ml / g, and the carbon monoxide / carbon dioxide ratio is 7.0 to 9.0.

The carbon black for electrodes of the present invention is preferably used as an electrode of a primary battery or a secondary battery among battery electrodes.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

The carbon black for electrodes of the battery or the electric double layer type capacitor of the present invention has a micropore width at which the maximum value of the micropore volume derived from the relationship curve between the micropore volume and the micropore width is reached. Is in the range of 4.0 to 8.0 angstroms. When the micropore width is 4.0 angstroms or more, the affinity with the electrolytic solution becomes good, and as a result, the battery and capacitor performance can be improved. When the micropore width is 8.0 angstroms or less, the dispersibility of carbon black is improved, and as a result, the battery and capacitor performance can be improved. In this case, the maximum value of the micropore volume is in the range of 0.060 ml / angstrom / g or more and 0.135 ml / angstrom / g or less. The maximum value of micropore volume is 0.060m
If it is 1 / Angstrom / g or more, the affinity with the electrolytic solution is good, and as a result, the battery performance is improved,
When it is 0.135 ml / angstrom / g or less, the dispersibility of carbon black is improved, and as a result, the battery and capacitor performance can be improved.
The maximum value of the micropore volume is preferably 0.075 to
0.135 ml / angstrom / g, and more preferably 0.090 to 0.135 ml / angstrom / g.
It is g.

From the viewpoint of further increasing the battery capacity, the micropore width at which the maximum value of the micropore volume derived from the relationship curve between the micropore volume and the micropore width of carbon black is 4.5 is 4.5. Is in the range of ~ 7.5 Å and the maximum micropore volume is 0.095.
It is preferably about 0.130 ml / angstrom / g. In particular, the micropore width is in the range of 5.0 to 7.0 angstrom and the maximum value of the micropore volume is 0.100 to 0.125 ml / angstrom /
It is preferably g.

The relationship curve between the micropore volume and the micropore width in the present invention is as follows, using an Autosoap 1-MP type manufactured by Canterchrome Co. (or an apparatus having a function equivalent thereto) may be used. It is the value measured by using.

The micropore volume and the micropore width are determined by adsorbing nitrogen gas at a liquid nitrogen temperature on a sample previously dried at 200 ° C. for 12 hours or more and adsorbing it on the sample surface under an adsorption equilibrium pressure of nitrogen. The adsorption / desorption isotherm is obtained from the amount of gas being stored, and the value on the adsorption side of the obtained isotherm is analyzed by the HK method.
It is determined by calculating the relationship between the micropore width and the micropore volume. The micropore width means that the carbon black may have micropores of 20 angstroms or less, and the fine pores are assumed to be slits by the HK method.

In the carbon black for electrodes of the battery or electric double layer type capacitor of the present invention, the total pore volume is preferably 3.5 to 5.0 ml / g, more preferably 4. It is 0 to 5.0 ml / g. When the total pore volume is 3.5 ml / g or more, the affinity with the electrolytic solution becomes good, and as a result, the battery and capacitor performance can be improved. Also 5.0 ml / g
In the following cases, the dispersibility of carbon black is good, and as a result, the battery and capacitor performance can be improved. To further increase the electric capacity, the total pore volume is preferably 4.1 to 4.9 ml / g, particularly preferably 4.2 to 4.8 ml / g.

The surface characteristics of carbon black are considered to vary depending on the kind and the amount of surface functional groups of carbon black, in addition to the above-mentioned pore characteristics. Therefore, in the present invention, the volatile matter (oxygen, hydrogen, carbon monoxide, carbon dioxide, etc.) generated when the carbon black is heated at a constant temperature is examined in detail, and the volatile matter and the surface characteristics of the carbon black are We found that there is a close relationship.
In particular, when used for electrodes of batteries or electric double layer type capacitors, CO / CO ₂ of volatile matter of carbon black at 950 ° C. is preferably in the range of 6.0 to 10.0. By setting CO / CO ₂ to 6.0 or more, the affinity with the binder such as vinylidene fluoride resin or tetrafluoroethylene used for batteries and capacitors is improved, and the high performance of batteries and electric double layer capacitors is achieved. The capacity can be increased. On the other hand, CO / CO ₂ of 10.
When it is 0 or less, the dispersibility of carbon black is improved, and as a result, the battery and capacitor performance can be improved. In order to further increase the capacity, CO / CO ₂ is more preferably 6.5 to 9.5, and particularly preferably 7.0 to 9.0.

The carbon black of the present invention is obtained by incompletely burning hydrocarbons such as gas furnace method, oil furnace method, degussa gas furnace method, acetylene method, thermal method, channel method, Texaco method, shell method and the like. Can be produced by using a general method for producing the above, by arbitrarily selecting the temperature, pressure and gas component in the furnace. Further, the carbon black produced by these methods and having properties other than the present invention can also be produced by subjecting it to a secondary treatment such as steam or high temperature.

Among them, a liquid hydrocarbon (carbon oil) in which carbon black is mixed with an aromatic liquid hydrocarbon,
Using A heavy oil, C heavy oil, or pyrolysis oil of naphtha as a feedstock oil, the temperature inside the furnace is 1200 to 1600 ° C., the pressure inside the furnace is 10 to 80 kg / cm ² , and the amount of steam supplied into the furnace is liquid. 200-1300k per ton of hydrocarbon
g of carbon black obtained by this method or in an inert atmosphere at 200 to 900
A method of secondary treatment at ℃ is preferred.

The carbon black of the present invention is used as an electrode composition of batteries and electric double layer type capacitors. Specifically, secondary batteries such as lithium batteries, manganese batteries, alkaline manganese batteries and other primary batteries, lithium ion batteries, lithium polymer batteries, zinc-air batteries, nickel-hydrogen batteries, polymer type batteries, sodium-sulfur batteries, zinc-bromine batteries, etc. Examples include secondary batteries and electric double layer capacitors.

The amount of carbon black used in the present invention is not particularly limited, but preferably positive or negative electrode active material 1
It is 0.1 to 25.0 parts by mass, more preferably 0.2 to 20.0 parts by mass, relative to 00 parts by mass.

As a method for producing an electrode using the carbon black of the present invention, a dispersion of carbon black is prepared in advance, and an active material, a binder and various additives are added to this dispersion and further dispersed, A method of coating and drying the current collector, carbon black, an active material, a binder, a method of simultaneously dispersing various additives in a solution, a method of coating and drying the current collector, carbon black, an active material, a binder, A method in which various additives are dispersed by a dry mixer and the binder is bound to the current collector by pressurization such as compression molding is used.

As the disperser, a known disperser such as a ball mill, a sand mill, a triple roll, a high speed disperser or the like used for preparing a coating material, a Henschel mixer, a planetary ball mill or the like dry mixer can be used. .

[0031]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

(Preparation of carbon black) Initial distillation temperature: 180 to 190 ° C., 10% distillation temperature: 205
~ 215 ° C, 50% distillation temperature: 250-260 ° C, 97
% Distillation temperature: A hydrocarbon having a temperature of 320 to 340 ° C. was used as a feed oil.

<Carbon Black B-1> In-furnace temperature: 1400 ° C., in-furnace pressure: 30 Kg / cm ² ,
The amount of steam supplied to the furnace is 50 with respect to the raw hydrocarbon.
The raw material hydrocarbon was reacted under the condition of 0 kg / ton to obtain carbon black B-1.

<Carbon Black B-2> Furnace temperature: 1500 ° C., furnace pressure: 30 Kg / cm ² ,
The amount of steam supplied to the furnace is 80 with respect to the raw hydrocarbons.
The raw material hydrocarbon was reacted under the condition of 0 kg / ton to obtain carbon black B-2.

<Carbon Black B-3> Furnace temperature: 1250 ° C., Furnace pressure: 30 Kg / cm ² ,
The amount of steam supplied to the furnace is 80 with respect to the raw hydrocarbons.
The raw material hydrocarbon was reacted under the condition of 0 kg / ton to obtain carbon black B-3.

<Carbon Black B-4> Furnace temperature: 1300 ° C., furnace pressure: 30 Kg / cm ² ,
The amount of steam supplied to the furnace is 10 with respect to the raw material hydrocarbon.
Raw material hydrocarbons were reacted under the condition of 00 kg / ton to obtain carbon black B-4.

<Carbon Black B-5> Furnace temperature: 1500 ° C., Furnace pressure: 30 Kg / cm ² ,
The amount of steam supplied to the furnace is 10 with respect to the raw material hydrocarbon.
The raw material hydrocarbon was reacted under the condition of 00 kg / ton to obtain carbon black B-5.

<Carbon Black B-6> In-furnace temperature: 1400 ° C., in-furnace pressure: 30 Kg / cm ² ,
The amount of steam supplied to the furnace is 80 with respect to the raw hydrocarbons.
The raw material hydrocarbon was reacted under the condition of 0 kg / ton to obtain carbon black B-6.

<Carbon Black B-7> In-furnace temperature: 1400 ° C., in-furnace pressure: 30 Kg / cm ² ,
The amount of steam supplied to the furnace is 11 with respect to the raw hydrocarbon.
The raw material hydrocarbon was reacted under the condition of 00 kg / ton to obtain carbon black B-7.

<Carbon Black B-8> In-furnace temperature: 1250 ° C., in-furnace pressure: 30 Kg / cm ² ,
The amount of steam supplied to the furnace is 80 with respect to the raw hydrocarbons.
The raw material hydrocarbon was reacted under the condition of 0 kg / ton to obtain carbon black. Carbon black B-8 was obtained by treating this carbon black in an N ₂ atmosphere at 600 ° C. for 5 hours.

The properties of the resulting carbon black are shown in Tables 1 and 2.

The carbon monoxide / carbon dioxide ratio (CO
/ CO ₂ ) was determined by heating carbon black to 950 ° C. under reduced pressure and quantifying the generated gas by gas chromatography.

The maximum micropore width (angstrom) and the maximum micropore volume (ml / angstrom / g) at which the micropore volume reaches the maximum value are the Autosoap 1-MP manufactured by Canterchrome Co. Using a mold, from the nitrogen adsorption isotherm, the relationship curve between the micropore width and the micropore volume was calculated and plotted by the HK method. The total pore volume (ml / g) was determined from the nitrogen adsorption isotherm.

[0044]

[Table 1] Properties B-1 B-2 B-3 B-4 CO / CO ₂ (-) 4.2 8.4 3.6 7.4 Pore width ^{* 1} 6.0 2.0 5.9 6.2 (angstrom) Maximum value of micropore volume 0.070 0.120 0.110 0.115 (ml / angstrom / g) Total pore volume (ml / g) 2.3 4.6 3.8 4.5 ^{* 1} ) Micropore width where the micropore volume reaches its maximum value

[0045]

TABLE 2 Typical Properties B-5 B-6 B- 7 B-8 CO / CO 2 (-) 9.1 8.2 8.3 8.2 pore width ^* 1 5.8 5.9 6. 0 6.2 (angstrom) Maximum value of micropore volume 0.113 0.098 0.127 0.110 (ml / angstrom / g) Total pore volume (ml / g) 4.6 4.2 4.2. 8 4.5 ^{* 1} ) Micropore width where the micropore volume reaches its maximum value

Denka black produced by Electrochemical Co., which is acetylene black, was used as a comparative example. Table 3 shows the properties of acetylene black (referred to as carbon black B-9).
Shown in.

[0047]

[Table 3] Properties Acetylene black (B-9) CO / CO ₂ (−) 44.0 Pore width ^{* 1} (angstrom) 6.1 Maximum value of micropore volume (ml / angstrom / g) 010 total pore volume (ml / g) 0.74 ^{* 1} ) Micropore width where the micropore volume reaches its maximum value

Example 1 Lithium Ion Secondary Battery A positive electrode for a lithium ion secondary battery was prepared as follows.
Lithium manganate (LiMn ₂ O ₄ ) 1 having a particle size distribution of about 0.1 μm to 100 μm, which is a positive electrode active material
Various carbon blacks having the compositions shown in Tables 4 and 5 were added to 100 parts by mass. To this, 10 parts by mass of polyvinylidene fluoride resin (PVDF) as a binder was added, and N-methylpyrrolidone (NM) was added as a dispersion solvent.
P) 200 parts by mass of the active material mixture slurry added and kneaded was applied to both sides of an aluminum foil that is a two-dimensional current collector having a thickness of 20 μm, and then dried, pressed and cut to obtain a positive electrode having a thickness of 200 μm.

The negative electrode was prepared as follows. PVDF as a binder is added to graphite powder 100
10 parts by mass with respect to parts by mass, 100 parts by mass of NMP as a dispersion solvent was added thereto, and the dispersed slurry was applied to both sides of a rolled copper foil having a thickness of 10 μm, which is a two-dimensional current collector, and then dried, pressed and cut. By doing so, a negative electrode having a thickness of 130 μm was obtained.

The positive electrode and the negative electrode produced by the above method were wound, and the wound group was housed in a cylindrical battery container via a polyethylene separator having a thickness of 25 μm to obtain a lithium ion secondary battery. As the electrolytic solution, a mixed solution of ethylene carbonate and dimethyl carbonate in which 1 mol / L of LiPF ₆ was dissolved was used. After caulking and sealing the upper lid, a predetermined amount of the electrolytic solution was injected through the injection port and sealed. The designed battery capacity of this battery is 1300 mAh.

The batteries manufactured as described above (Nos. 1 to 1)
Regarding 3), the discharge capacity and heavy load characteristics were measured. In the discharge capacity test, the battery was charged at a constant current for 8 hours at a rate (1 / 8C) for 8 hours, and then discharged at 1 / 8C to a final voltage of 3.2V. Table 4 shows the discharge capacity of each battery under these conditions.
As for the discharge capacity, the discharge capacity of the example (No. 1) in Table 4 was 10
The ratio (%) when 0% is indicated. The heavy load characteristics are
After the initial capacity test, after the charge and discharge efficiency became stable, 1 at constant current
/ 8C charge for 8 hours, discharge 1 / 8C, end voltage =
Similarly to the discharge capacity (X) when implemented at 3.2V,
The discharge capacity (Y) was measured when the battery was discharged at a rate of / 2 hours (2C) and the final voltage was 3.2V. 2C discharge capacity ratio to 1 / 8C discharge and Y / X (%) are shown in Tables 4 and 5 as indexes of heavy load characteristics. It can be said that the larger this value is, the more excellent the heavy load characteristic is.

[0052]

[Table 4] Positive electrode composition (parts by mass) Discharge capacity Heavy load characteristics No. B-4 B-5 B-6 B-7 B-8 Active material PVDF (%) (%) 1 3.0 − − − − 100 10 100 88 2 − 3.0 − − − 100 10 105 90 90 3 7.0 − − − − 100 10 110 92 4 4 − − 3.0 − − 100 10 95 9 87 5 − − − 3.0 − 100 10 115 115 3 36 − − − − 3.0 100 10 110 9 91 7 − − 7.0 − − 100 10 105 105 89 8 − − − 0.5 − 100 10 95 86

[0053]

[Table 5] Positive electrode composition (parts by mass) Discharge capacity Heavy load characteristics No. B-1 B-2 B-3 B-9 Active material PVDF (%) (%) 9 3.0 − − − 100 10 78 78 78 10 − 3.0 − − 100 10 60 50 50 11 − − 3.0 − 100 10 82 83 12 − 12 − − − 3.0 100 10 52 44 13 − − − 10.0 100 10 60 50

As is clear from Tables 4 and 5, the lithium ion secondary battery containing the carbon black of the present invention in the positive electrode has a high discharge capacity and an excellent heavy load characteristic.
On the other hand, it is understood that the lithium ion secondary battery containing carbon black other than the present invention in the positive electrode is inferior in both discharge capacity and heavy load characteristics.

(Example 2: Nickel-hydrogen secondary battery) A negative electrode of a nickel-hydrogen secondary battery was prepared as follows. 100 parts by mass of Misch metal nickel alloy (AB ₅ alloy) powder as a hydrogen storage alloy which is an active material, and dispersions of various carbon blacks and polytetrafluoroethylene (PTFE) shown in Tables 6 and 7 in solid content. 1.5 parts by mass, carboxymethyl cellulose (CMC)
0.5 part by mass was dispersed in 200 parts by mass of water to prepare a paste. The obtained paste was applied to a nickel-plated punching metal serving as a current collector, dried at 80 ° C., the thickness was adjusted by a roll press, and then cut into a predetermined size to prepare a negative electrode.

The positive electrode of the nickel-hydrogen secondary battery was produced as follows. 100 parts by mass of nickel hydroxide powder, 6 parts by mass of cobalt oxide, 3.0 parts by mass of PTFE dispersion in solid content, 1.0 part by mass of CMC were dispersed in 200 parts of water to prepare a paste. The obtained paste was applied and impregnated on a foam metal serving as a current collector, dried, and then cut into a predetermined size to prepare a positive electrode.

A nylon non-woven fabric separator was sandwiched between the positive electrode and the negative electrode, wound in a spiral shape, and inserted into an AA size battery can. Then, a 31% by mass aqueous potassium hydroxide solution was injected as an electrolytic solution to obtain a rating. A sealed cylindrical battery (No. 17 to 29) having a capacity of 1000 mAh was produced. 1 test battery
After charging 150% with C, set the cutoff voltage to 1.0V and discharge at 1C, measure the discharge capacity, and repeat the same charging / discharging up to 500 times, the capacity is 70% of the initial value.
The number of discharges until reaching (700 mAh) was measured and used as the value of cycle characteristics. These measurement results are shown in Table 6 and Table 7.
Shown in. The cycle characteristics of the battery that could maintain 70% or more at the time of 500 times were marked as ◯, and the cycle characteristics of the battery that decreased to 50% or less were marked as x. Further, the discharge capacity is shown as a ratio (%) when the discharge capacity of the example (No. 17) in Table 6 is 100%.

[0058]

[Table 6] Negative electrode composition (parts by mass) Discharge capacity Cycle No. B-4 B-5 B-6 B-7 Active material CMC PTFE (%) Characteristic 17 0.5 − − − 100 0.5 1.5 100 ○ 18 − 0.5 − − 100 0.5 1.5 103 ○ 19 5.0 − − − 100 0.5 1.5 108 ○ 20 − − 0.5 − 100 0.5 1.5 98 ○ 21 − − − 0.5 100 0.5 1.5 112 ○ 22 − − − 3.0 100 0.5 1.5 110 ○ 23 − − 5.0 − 100 0.5 1.5 103 ○ 24 − 2.0 − − 100 0.5 1.5 104 ○

[0059]

[Table 7] Negative electrode composition (parts by mass) Discharge capacity Cycle No. B-1 B-2 B-3 B-9 Active material CMC PTFE (%) Characteristics 25 0.5 − − − 100 0.5 1.5 81 ○ 26 − 0.5 − − 100 0.5 1.5 64 × 27 − − 0.5 − 100 0.5 1.5 85 ○ 28 − − − 0.5 100 0.5 1.5 58 × 29 − − − 5.0 100 0.5 1.5 66 ×

As is clear from Tables 6 and 7, the nickel-hydrogen battery containing the carbon black of the present invention in the negative electrode is
It has a high discharge capacity and excellent cycle characteristics. On the other hand, it can be seen that the nickel-hydrogen battery containing carbon black other than the present invention in the negative electrode is inferior in discharge capacity and cycle characteristics.

Example 3 Electric Double Layer Capacitor Phenolic Solvent KOH Activated Activated Carbon Powder (Specific Surface Area 1950 m ² / g, Average Particle Size 10 μm) as Active Material,
To a mixture of 10 parts by mass of various carbon blacks and polytetrafluoroethylene (PTFE), 5 parts by mass of ethanol was added, kneaded, and rolled to obtain a width of 10 cm.
Make a sheet with a length of 10 cm and a thickness of 0.65 mm, and
It was dried at 00 ° C. for 2 hours.

A polarizable electrode obtained by punching out the above sheet to a diameter of 12 mm was made of stainless steel 31 with a graphite-based conductive adhesive.
It was adhered to the case and lid of the No. 6 container and used as the positive electrode and the negative electrode. 3 covers and case with polarizable electrodes attached
After drying for 4 hours under reduced pressure at 00 ° C., it was transferred into a glove box under an argon atmosphere, the electrode was impregnated with a propylene carbonate solution containing 1 mol / liter of tetraethylammonium tetrafluoroborate, and a polypropylene non-woven fabric separator was used. Both electrodes were made to face each other and caulked and sealed in a container using an insulating gasket made of polypropylene. The obtained coin type electric double layer capacitor has a diameter of 18.3 mm and a thickness of 2.0 mm.

The initial electrostatic capacitance (F) when the obtained coin type electric double layer capacitors (No. 30 to 42) were charged with an applied voltage of 2.5 (V) and discharged at about 0.5 mA. It was measured. Further, the same charge / discharge can be performed up to 1000
Repeated times, the number of discharges until the capacity reached 70% of the initial value was measured and used as the value of cycle characteristics. The results of these measurements are shown in Tables 8 and 9. 70% at 1000 times
The cycle characteristics of the battery capable of maintaining the above are marked with ◯, and the cycle characteristics of the electric double layer capacitor reduced to 50% or less are marked with x.

[0064]

[Table 8] Electrode composition (parts by mass) Capacitance cycle No. B-4 B-5 B-6 B-7 B-8 Active material PTFE (F) Characteristics 30 10 − − − − 80 10 3.0 ○ 31 − 10 − − − 80 10 3.1 ○ 32 20 − − − − 80 10 3.2 ○ 33 − − 10 − − 80 10 2.9 ○ 34 − − − 10 − 80 10 3.3 ○ 35 − − − − 80 80 10 3.2 ○ 36 − − 15 − − 80 10 3.0 ○ 37 − − − 5 − 80 10 2.9 ○

[0065]

[Table 9] Electrode composition (parts by mass) Capacitance cycle No. B-1 B-2 B-3 B-9 Active material PTFE (F) Characteristic 38 10 − − − 80 10 2.5 ○ 39 −10 − − 80 10 2.3 × 40 − − 10 − 80 10 2. 6 ○ 41 − − − 5 80 10 2.0 × 42 − − − 15 80 10 2.2 ×

From Tables 8 and 9, it can be seen that by using the carbon black of the present invention, an electric double layer type capacitor having excellent capacitance and cycle characteristics can be obtained.

(Example 4: Lithium-manganese dioxide primary battery) 100 parts by mass of electrolytic manganese dioxide, various carbon blacks and polytetrafluoroethylene (PTF).
E) 5 parts by mass were kneaded to prepare a positive electrode mixture. Further, metallic lithium was cut into a size of 15 mm in diameter and 0.25 mm in thickness to obtain a negative electrode body.

Further, the positive electrode mixture described above was attached to a positive electrode can made of stainless steel, and a polypropylene nonwoven fabric as a separator was placed thereon, and then LiClO ₄ was dehydrated at a concentration of 1 mol / L in propylene. Carbonate and 1,2
A non-aqueous electrolyte solution dissolved in a mixed solvent of dimethoxyethane (volume ratio 1: 1) was impregnated. The negative electrode body is placed thereon to form a power generating element, and the battery (No. 43 to
55) was prepared.

A constant resistance discharge of 1 kΩ was performed on this battery to determine the discharge capacity. The results are shown in Table 10 and Table 11.
Shown in. The discharge capacities are shown in Table 10 (Example No. 4).
It is shown as a ratio (%) when the discharge capacity of 3) is 100%.

[0070]

[Table 10] Positive electrode composition (parts by mass) Discharge capacity No. B-4 B-5 B-6 B-7 B-8 Active material PTFE (%) 435 − − − − 100 5 100 44 − 5 − − − 100 5 102 45 10 − − − − 100 5 107 46 − − 5 − − 100 5 97 47 − − − − 5 − 100 5 111 48 − − − − 5 100 5 108 49 − − 15 − − 100 5 108 50 − − − 3 − 100 5 95

[0071]

Table 11 Positive electrode composition (parts by mass) Discharge capacity No. B-1 B-2 B-3 B-9 Active material PTFE (%) 51 5 − − − 100 5 86 52 − 5 − − 100 5 68 53 − − 5 − 100 5 88 54 − − − 5 100 5 58 55 − − − 15 100 5 66

From Tables 10 and 11, the use of the carbon black of the present invention makes it possible to obtain a lithium-based battery having excellent discharge capacity.
It can be seen that a manganese dioxide primary battery can be obtained.

[0073]

As described above, according to the present invention,
The micropore width derived from the relationship curve between the micropore volume and the micropore width of carbon black is the maximum value, and the maximum micropore volume is constant. By using a specific carbon black within the range as an electrode composition of a battery or an electric double layer type capacitor, a battery or an electric double layer type capacitor excellent in capacity, heavy load characteristics and cycle characteristics can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01G 9/058 H01G 9/00 301A (72) Inventor Masaaki Mizuta 1-12-8 Ryogoku, Sumida-ku, Tokyo F-term in Muneka Waviru Ketjen Black International Co., Ltd. (reference) 4G146 AA01 4J037 BB05 BB15 BB28 BB31 5H050 AA02 AA07 AA08 BA06 BA14 BA17 CA03 CA05 CA09 CB08 CB12 CB17 DA10 EA10 HA01 HA06 HA07

Claims (9)

[Claims] 1. A carbon black used as an electrode composition of a battery or an electric double layer type capacitor, comprising:
The micropore width where the maximum value of the micropore volume derived from the relational curve of the micropore volume and the micropore width is in the range of 4.0 to 8.0 angstrom, and the micropore volume is The maximum value of 0.060-0.135 ml
Carbon black for electrodes of batteries or electric double layer type capacitors, characterized in that it is / angstrom / g. 2. The maximum value of the micropore volume is 0.0
The carbon black for an electrode of a battery or an electric double layer type capacitor according to claim 1, which has an amount of 75 to 0.135 ml / angstrom / g. 3. The maximum value of the micropore volume is 0.0
The carbon black for an electrode of a battery or an electric double layer type capacitor according to claim 1, wherein the carbon black is 90 to 0.135 ml / angstrom / g. 4. The total pore volume is 3.5 to 5.0 ml / g.
The carbon black for an electrode of a battery or an electric double layer type capacitor according to any one of claims 1 to 3. 5. The total pore volume is 4.0 to 5.0 ml / g.
The carbon black for an electrode of a battery or an electric double layer type capacitor according to any one of claims 1 to 3. 6. Carbon monoxide having a volatile content at 950 ° C. /
The ratio of carbon dioxide is 6.0 to 10.0.
5. Carbon black for electrodes of the battery or electric double layer type capacitor according to any one of 5 above. 7. The micropore width is in the range of 4.5 to 7.5 angstroms, and the maximum micropore volume is 0.095 to 0.130 ml / angstrom /
7. The total pore volume in g is 4.1 to 4.9 ml / g and the carbon monoxide / carbon dioxide ratio is 6.5 to 9.5. Carbon black for electrodes of batteries or electric double layer capacitors. 8. The micropore width is in the range of 5.0 to 7.0 angstroms, and the maximum value of the micropore volume is 0.100 to 0.125 ml / angstrom / g. Pore volume is 4.2-4.8 ml / g,
The carbon black for an electrode of a battery or an electric double layer type capacitor according to claim 1, wherein the carbon monoxide / carbon dioxide ratio is 7.0 to 9.0. 9. The carbon black for an electrode of a battery or an electric double layer type capacitor according to claim 1, wherein the battery is a primary battery or a secondary battery.